US6946541B2 - Composition based on renewable raw materials - Google Patents

Composition based on renewable raw materials Download PDF

Info

Publication number
US6946541B2
US6946541B2 US10/296,520 US29652004A US6946541B2 US 6946541 B2 US6946541 B2 US 6946541B2 US 29652004 A US29652004 A US 29652004A US 6946541 B2 US6946541 B2 US 6946541B2
Authority
US
United States
Prior art keywords
acid
composition according
mixture
tin
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US10/296,520
Other languages
English (en)
Other versions
US20040152864A1 (en
Inventor
Milko Ess
Bernd Kastl
Siegfried Reichert
Hanns-Jörg Mauk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DLW AG
Original Assignee
DLW AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP00116781A external-priority patent/EP1178065A1/fr
Application filed by DLW AG filed Critical DLW AG
Assigned to DLW AKTIENGESELLSCHAFT reassignment DLW AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MAUK, HANNS-JORG, ESS, MILKO, KASTL, BERND, REICHERT, SIEGFRIED
Publication of US20040152864A1 publication Critical patent/US20040152864A1/en
Application granted granted Critical
Publication of US6946541B2 publication Critical patent/US6946541B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/027—Polycondensates containing more than one epoxy group per molecule obtained by epoxidation of unsaturated precursor, e.g. polymer or monomer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/681—Metal alcoholates, phenolates or carboxylates

Definitions

  • the present invention relates to a composition based on renewable raw materials which is particularly characterized by containing at least one tin-containing compound, an article made thereof as well as a process for the preparation of such an article.
  • the composition according to the present invention exhibits an increased curing rate, i.e. a shortened “incubation time”, compared to those compositions based on renewable raw materials currently available in the prior art.
  • the composition according to the present invention can advantageously used particularly in casting and rotational casting processes, respectively.
  • compositions based on renewable raw materials are frequently used for coating masses of planar structures as it is e.g. known from DE-A41 35 664.
  • the coating masses consist of a combination of epoxidation products of esters of unsaturated fatty acids and partial esters of polycarboxylic acids with polyether polyols as well as a hydrophobing agent. These coating masses are particularly used for the production of floor coverings.
  • composition comprising the reaction product of at least one dicarboxylic acid or one polycarboxylic acid or derivatives thereof or a mixture thereof with at least one epoxidation product of a carboxylic acid ester or a mixture of said epoxidation product in the presence of at least one tin-containing compound.
  • the composition according to the present invention exhibits a shortened “incubation time” and “reaction time”, respectively, over the currently available compositions based on renewable raw materials.
  • incubation time means the time period from the beginning of adding the cross-linking agent, i.e. the at least one dicarboxylic acid or one polycarboxylic acid or derivatives thereof or a mixture thereof constituting the specific reaction product of which the composition of the present invention is comprised, until the moment when the viscosity of the mass begins to increase, i.e. a rising in a diagram wherein the viscosity of the mass, for example measured by a conventional Haake viscosimeter, is plotted against the time.
  • the specific use of a tin-containing compound surprisingly gives rise to a remarkably increased curing rate.
  • the increased curing rate can be proven by measuring the gel point according to ASTM D 4473 using dynamic-mechanical oscillation instrumentation for reporting the cure behaviour of such compositions.
  • this particular characteristic advantageously enables the processing of the composition according to the present invention by casting and rotational casting, respectively.
  • FIG. 1 shows the result of the measurements, wherein the elastic and viscous moduli of specimens made of a composition according to the present invention and a currently available prior art composition based on renewable raw materials, respectively, are plotted as a function of time to determine the gel point according to ASTM D 4473 in order to evaluate the cure behaviour.
  • the tin-containing compound is selected from the group consisting of organotin compounds, tin salts and tin chelates.
  • Preferred examples of the tin-containing compounds are organotin (II) compounds of C 6 to C 18 aliphatic or cycloaliphatic monocarboxylic acids, such as for example stannous diethylhexanoate, stannous dioctoate, or stannous dilaureate, or organotin (IV) compounds of C 6 to C 18 aliphatic or cycloaliphatic monocarboxylic acids, such as for example dibutyltin dilaureate or tributyltin octoate.
  • the tin-containing compound(s) is (are) present in an amount ranging from 0.01 to 5 wt.-%, more preferably 0.01 to 1 wt.-%, based on the total amount of said composition.
  • Maleic acid, itaconic acid, fumaric acid, succinic acid, methylsuccinic acid, malic acid, furandicarboxylic acid, phthalic acid, tartaric acid, or citraconic acid, or a mixture thereof containing at least two of these acids can preferably be used as dicarboxylic acid.
  • Acids with three or more carboxyl groups such as, for example, citric acid, aconitic acid and trimellitic acid can preferably be used as polycarboxylic acids.
  • Anhydrides or partial esters or derivatives having at least one free carboxyl group can be used as derivatives of the dicarboxylic acids or polycarboxylic acids.
  • the alcohol component of the partial esters is not subject to special restriction, but polyols such as dipropylene glycol, propanediols, butanediols, hexanediols, hexanetriols, pentaerythritol or glycerin are preferably used as alcohol component.
  • a composition comprising the reaction product of at least one epoxidation product of a carboxylic acid ester or a mixture of said epoxidation product with a mixture of a partial ester of a di- or polycarboxylic acid and a polycarboxylic acid having three or more carboxylic acid groups, in the presence of at least one tin-containing compound.
  • a mixture of a partial ester of maleic anhydride and dipropylene glycol together with citric acid is used as crosslinking agent.
  • the content of citric acid is up to 50 percent by weight, more preferably up to 25 percent by weight, relative to the total quantity of crosslinking agent.
  • the epoxidation product of a carboxylic acid ester of which the composition of the present invention is further comprised preferably contains more than one epoxy group per molecule.
  • Epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized rape-seed oil or vernonia oil or a mixture thereof containing at least two of these epoxidized products can preferably be used as epoxidation product of a carboxylic acid ester.
  • the afore-defined alcohols of the partial esters such as, for example, dipropylene glycol, propanediols, butanediols, hexanediols, hexanetriols, pentaerythritol, or glycerin can also be used as alcohol component of these carboxylic acid esters.
  • the carboxylic acid component is not subject to special restriction.
  • the quantities by weight of crosslinking agent and epoxidation product are each preferably 5 to 85 percent by weight, relative to the total quantity of the composition.
  • the composition according to the present invention can further comprise at least one additive selected from the group consisting of fillers, pigments, expanding agents, hydrophobing agents and auxiliary substances.
  • the filler is wood dust, chalk, cellulose, lignin or cork dust, or a mixture thereof containing at least two of these substances.
  • the auxiliary substance can, for example, be selected from the group consisting of tall oils, synthetic or natural resins, and siccatives.
  • the composition according to the present invention preferably comprises 15 to 98 percent by weight of the reaction product and 2 to 85 percent by weight of at least one filler, relative to the total quantity of the composition.
  • a further subject of the present invention is an article made of the composition as specified hereinbefore.
  • the article according to the present invention can have any desired shape, depending on the specific purposes only.
  • composition according to the invention can also be prepared in the form of prepolymers, in which either the crosslinking agent or the epoxidation product can be present in deficiency.
  • prepolymers are stable in storage and exhibit partly thermoplastic properties.
  • the weight ratio of crosslinking agent to epoxidation product in these prepolymers preferably lies in the range from 10:1 to 1:20.
  • These prepolymers of the composition according to the present invention are then converted into the completely crosslinked material in a subsequent step only, optionally with the addition of the component present in deficiency as well as optionally further additives.
  • Such prepolymers made of the composition according to the present invention can particularly be used in injection molding processes when for example pellets composed of those prepolymers are melted by the combined action of external heating and internal friction caused by the transport of the material by single or twin screws.
  • the “incubation time” in said process is less than 10 minutes.
  • step (c) can be carried out
  • the UV initiators used may be radical or cationic UV initiators, or a mixture of said types of UV initiators.
  • radical UV initiators are benzophenone, benzophenone derivatives, phosphine oxides, ⁇ -morpholino ketones, quinone, quinone derivatives or ⁇ -hydroxy ketones, or mixtures thereof.
  • cationic UV initiators are triarylsulfonium salts which may be of one type or a mixture of different triarylsulfonium salts, or diaryliodonium salts, or mixtures thereof.
  • Said UV initiators may be present, for example, in an amount up to 8% by weight, preferably 0.1 to 3% by weight, based on the composition.
  • at least one photosensitizer may be present, such as e.g. compounds based on anthracene, perylene or thioxanthene-9-one, which is able to activate the UV initiator and to enhance the effectiveness thereof, thereby reducing the concentration of the UV initiator.
  • UV radiation employed is, generally, within the usual range, i.e. 200 nm to 380 nm.
  • IR radiation employed is, generally, within the usual range, for example, 760 nm to 0.5 mm.
  • composition according to the present invention can be processed by casting and rotational casting processes, respectively, to obtain respective articles made thereof, but injection moulding is also possible.
  • Casting requires liquid compounds or prepolymers which are polymerized or crosslinked after being poured into open forms. Accordingly, when performing a casting process by using the composition according to the present invention, said composition can be processed directly to finished articles at elevated temperatures (hot-curing systems) or room temperatures (cold-curing systems). Thick-walled articles, embeddings, sheets, blocks, and rods made of the composition according to the present invention can be produced by such a process. Adequate temperature regulation is necessary to avoid thermal stresses. Apart from metal moulds with cooling channels, simpler moulds made of sheet metal, wood, ceramic, or glass can be used. To guarantee ease of release and to ensure smooth moulding surfaces, those parts of the mould that come in contact with the composition of the present invention should be sealed by coating or impregnating with conventional means known in the art.
  • Hollow articles made of the composition according to the present invention can be produced by e.g. rotational casting.
  • the mould is rotated about two perpendicular axes, causing uniform wetting of the cavity surface.
  • the two axes should be rotated at (usually adjustable) different speeds.
  • the individual process steps for example, filling and closing the mould, rotating in an oven, cooling, and removal of the moulding) are well-known to a person skilled in the art, and can be performed at separate stations.
  • Such rotational casting processes are well known in the prior art and, for example, described in DE-OS-23 43 045, DE-A-1 454 975 and DE-A1-40 32 540.
  • a rotational casting process using the composition according to the present invention is advantageous due to low investment costs and the ability to manufacture mouldings of various dimensions without pinch or weld seams, virtually free of stresses and with constant wall thicknesses.
  • the process for the production of the afore-mentioned article can also be performed as a two-stage process, wherein a prepolymer is first prepared in a first stage by mixing of crosslinking agent and epoxidation product with one of these components in deficiency, together with the specifically used tin-containing compound.
  • a prepolymer is first prepared in a first stage by mixing of crosslinking agent and epoxidation product with one of these components in deficiency, together with the specifically used tin-containing compound.
  • the weight ratio of crosslinking agent to epoxidation product in the first stage preferably lies in the range from 10:1 to 1:20.
  • the prepolymer obtained in this way can be press-molded and granulated, by which means a granular product is obtained that is stable in storage and is still partly thermoplastic as a result of the composition with one component in deficiency.
  • the partly thermoplastic granular product made of the prepolymer can then be shaped into a desired article and completely crosslinked optionally with the addition of the component present in deficiency in the first stage as well as optionally further additives.
  • Such a two stage process is particularly advantageous when the composition according to the present invention should be processed by injection molding processes to e.g operate on the batch principle.
  • compositions according to the present invention as well as a conventional composition based on renewable raw materials and a conventional composition based on renewable raw materials containing a Ba siccative but the latter compositions both without a tin containing compound, were prepared and evaluated.
  • Table 1 shows the influence of the specifically used tin-containing compound on the curing rate/“incubation time” measured at a temperature of 70° C.:
  • the siccatives used are each octoates of the metalls as indicated.
  • the respective numbers represent the % metall content.
  • “Incubation time” means the time period from the beginning of adding the cross-linking agent until the moment when the viscosity of the mass begins to increase.
  • Example 2 the viscoelastic properties of the above Example 2 and the Comparative Example were measured by using a Bohlin measuring instrument under oscillating frequency conditions of 2 Hz at 70° C.
  • the elastic (G′) and viscous (G′′) moduli (in Pascal (Pa)) are measured in shear as a function of time (in seconds).
  • FIG. 1 shows the result of measurements, where the moduli are plotted as a function of time.
  • Table 2 The results are given in the following Table 2.
  • Example 2 that is a composition according to the present invention, reaches the gel point measured according to ASTM D 4473 much quicker than the respective Comparative Example that is a composition based on renewable raw material currently available in the prior art. Accordingly, Example 2 exhibits an increased curing rate, when compared with said Comparative Example.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Detergent Compositions (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Disintegrating Or Milling (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Ink Jet (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
US10/296,520 2000-05-24 2001-05-21 Composition based on renewable raw materials Expired - Fee Related US6946541B2 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
EP00110902.4 2000-05-24
EP00110902 2000-05-24
EP00116781.6 2000-08-03
EP00116781A EP1178065A1 (fr) 2000-08-03 2000-08-03 Composition à base de matières premières renouvelables
PCT/EP2001/005823 WO2001090211A1 (fr) 2000-05-24 2001-05-21 Composition basee sur des matieres premieres renouvelables

Publications (2)

Publication Number Publication Date
US20040152864A1 US20040152864A1 (en) 2004-08-05
US6946541B2 true US6946541B2 (en) 2005-09-20

Family

ID=26070975

Family Applications (1)

Application Number Title Priority Date Filing Date
US10/296,520 Expired - Fee Related US6946541B2 (en) 2000-05-24 2001-05-21 Composition based on renewable raw materials

Country Status (7)

Country Link
US (1) US6946541B2 (fr)
EP (1) EP1285015B1 (fr)
AT (1) ATE315600T1 (fr)
AU (1) AU2001279624A1 (fr)
CA (1) CA2410036C (fr)
DE (1) DE60116638T9 (fr)
WO (1) WO2001090211A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050089690A1 (en) * 1999-07-21 2005-04-28 Bernd Fischer Storable moldable material and flat articles produced from renewable raw materials
US20090250962A1 (en) * 2008-04-08 2009-10-08 Gm Global Technology Operations, Inc. Deployable storage system for a vehicle bed
WO2021105513A1 (fr) * 2019-11-28 2021-06-03 Orineo BV Revêtement de résine époxydique durcie

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201360A (en) 1959-12-24 1965-08-17 Union Carbide Corp Curable mixtures comprising epoxide compositions and divalent tin salts
US3485573A (en) * 1965-05-20 1969-12-23 Boehme Chem Fab Kg Fat liquoring agent consisting of an epoxy compound and an acid containing ester
US3770675A (en) * 1967-11-16 1973-11-06 Ashland Oil Inc Curable epoxidized fatty compound polyester coating composition
US3943082A (en) * 1974-12-04 1976-03-09 Union Carbide Corporation Thermosetting powder coatings
US4119593A (en) 1977-05-18 1978-10-10 Union Carbide Corporation Polyepoxide high solids coatings
US4694033A (en) * 1984-08-09 1987-09-15 Dsm Resins B.V. Resin composition and process for the preparation of this resin composition
US5324846A (en) * 1992-01-30 1994-06-28 Elf Atochem North America, Inc. Partial esters of epoxy containing compounds
DE19627165A1 (de) 1995-07-05 1997-01-09 Preform Gmbh Polymerwerkstoff, Verfahren zu seiner Herstellung und dessen Verwendung
WO1998028356A1 (fr) 1996-12-24 1998-07-02 Dlw Aktiengesellschaft Materiau contenant des produits de polyreaction, et son procede de production
US20010023276A1 (en) * 1995-07-05 2001-09-20 Uwe Schoenfeld Polymeric material, method for its manufacture, and its utilization

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3201360A (en) 1959-12-24 1965-08-17 Union Carbide Corp Curable mixtures comprising epoxide compositions and divalent tin salts
US3485573A (en) * 1965-05-20 1969-12-23 Boehme Chem Fab Kg Fat liquoring agent consisting of an epoxy compound and an acid containing ester
US3770675A (en) * 1967-11-16 1973-11-06 Ashland Oil Inc Curable epoxidized fatty compound polyester coating composition
US3943082A (en) * 1974-12-04 1976-03-09 Union Carbide Corporation Thermosetting powder coatings
US4119593A (en) 1977-05-18 1978-10-10 Union Carbide Corporation Polyepoxide high solids coatings
US4694033A (en) * 1984-08-09 1987-09-15 Dsm Resins B.V. Resin composition and process for the preparation of this resin composition
US5324846A (en) * 1992-01-30 1994-06-28 Elf Atochem North America, Inc. Partial esters of epoxy containing compounds
DE19627165A1 (de) 1995-07-05 1997-01-09 Preform Gmbh Polymerwerkstoff, Verfahren zu seiner Herstellung und dessen Verwendung
US20010023276A1 (en) * 1995-07-05 2001-09-20 Uwe Schoenfeld Polymeric material, method for its manufacture, and its utilization
WO1998028356A1 (fr) 1996-12-24 1998-07-02 Dlw Aktiengesellschaft Materiau contenant des produits de polyreaction, et son procede de production
US6150436A (en) * 1996-12-24 2000-11-21 Dlw Aktiengesellschaft Material containing polyreactions products and method for the production thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050089690A1 (en) * 1999-07-21 2005-04-28 Bernd Fischer Storable moldable material and flat articles produced from renewable raw materials
US7482396B2 (en) * 1999-07-21 2009-01-27 Dlw Aktiengesellschaft Storable moldable material and flat articles produced from renewable raw materials
US20090250962A1 (en) * 2008-04-08 2009-10-08 Gm Global Technology Operations, Inc. Deployable storage system for a vehicle bed
WO2021105513A1 (fr) * 2019-11-28 2021-06-03 Orineo BV Revêtement de résine époxydique durcie
BE1027800B1 (nl) * 2019-11-28 2021-06-28 Orineo BV Coating van uitgehard epoxyhars

Also Published As

Publication number Publication date
EP1285015B1 (fr) 2006-01-11
ATE315600T1 (de) 2006-02-15
AU2001279624A1 (en) 2001-12-03
EP1285015A1 (fr) 2003-02-26
CA2410036A1 (fr) 2001-11-29
DE60116638D1 (de) 2006-04-06
US20040152864A1 (en) 2004-08-05
CA2410036C (fr) 2009-06-30
WO2001090211A1 (fr) 2001-11-29
DE60116638T2 (de) 2006-09-07
DE60116638T9 (de) 2012-01-12

Similar Documents

Publication Publication Date Title
US2255313A (en) Ethylenic-alpha-beta synthetic resins and process of making same
US4020122A (en) Process for the preparation of polyester compositions having increased melt elasticity
US4066625A (en) Unitary curable resin compositions
AU2016250029A1 (en) RMA crosslinkable compositions and RMA crosslinkable resins for easy to clean coatings
CN101570413A (zh) 亚克力人造石及其制备方法
US6946541B2 (en) Composition based on renewable raw materials
AU729857B2 (en) Materials containing polyreaction products and method for the production thereof
EP1178065A1 (fr) Composition à base de matières premières renouvelables
US3879319A (en) Silicone resin molding compositions
JPS6254338B2 (fr)
US2487105A (en) Composition capable of being molded and being cast into films
US2558047A (en) Cellulose derivative plastic composition
JPH02189321A (ja) 硬化性ポリウレタン注型用系及びそのためのアミン硬化剤
US1720051A (en) Plastic composition
US2665263A (en) Preparation of improved polymerizable unsaturated polyester compositions and polymerized material therefrom
CN110305569B (zh) 一种基于苯基丁二酸酐的聚酯树脂及其制备方法
US2648652A (en) Plasticized polyvinyl chlorides
US4311814A (en) Unsaturated polyester resin and process
EP0690110A1 (fr) Compositions de résines polyester en poudre
US2607756A (en) Polyesters stabilized with 1-arylazo-naphthol sulfonic acids
US3538042A (en) Epoxy resin moulding compositions containing phenolphthalein epoxy resin
EP0481041B1 (fr) Compositions d'ester de citrate et procedes de preparation
US3336248A (en) Urea formaldehyde-alpha cellulose-di-methyl siloxane polymer-molding compositions and method of manufacture
US3287297A (en) Coating compositions comprising vinyl chloride polymers and drying oil acid esters of liquid polyepoxides
US2853468A (en) Epoxy ether resin-polymethoxy acetal compositions

Legal Events

Date Code Title Description
AS Assignment

Owner name: DLW AKTIENGESELLSCHAFT, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ESS, MILKO;KASTL, BERND;REICHERT, SIEGFRIED;AND OTHERS;REEL/FRAME:014959/0489;SIGNING DATES FROM 20030319 TO 20040123

FPAY Fee payment

Year of fee payment: 4

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20130920